Compositions for dyeing keratinous fibres, containing pyrrolo-azoles; use as couplers; method of dyeing

ABSTRACT

The present invention relates to a composition for the dyeing of keratinous fibres, especially human hair, which comprises, in a medium appropriate for dyeing:  
     as coupler, at least one compound corresponding to one of the formulae:  
                 
 
     in which R 1  is especially hydrogen, halogen, aryloxy, alkoxy, acyloxy, arylthio, alkylthio, heteroarylthio, heteroaryloxy, etc;  
     R 2  and R 3  are independent and are especially hydrogen, halogen, alkyl, aryl, alkylthio, arylthio, benzylthio, etc;  
     Z a , Z b  and Z c  are independent and are a nitrogen atom or a carbon atom carrying a radical R 4 , R 5 , R 6  or R 7 ;  
     R 4 , R 6  and R 7  are identical or different and are especially hydrogen, alkyl, aryl, a heterocycle, a halogen, etc; and  
     R 5  is especially hydrogen, halogen, acyl, acyloxy or carbamoyl, etc;  
     and at least one oxidation base.

[0001] The invention relates to a composition for the dyeing ofkeratinous fibres, especially human hair, which comprises at least onepyrrolo-azole compound as coupler and at least one oxidation base.

[0002] It is known to dye keratinous fibres, and especially human hair,with dyeing compositions comprising oxidation dye precursors, especiallyortho- or para-phenylenediamines, ortho- or para-aminophenols andheterocyclic compounds, which are referred to generally as oxidationbases. The oxidation dye precursors, or oxidation bases, are colourlessor slightly coloured compounds which, when combined with oxidizingproducts, are able to give rise to coloured compounds and dyes by aprocess of oxidative condensation.

[0003] It is also known that the shades obtained with these oxidationbases can be varied by combining them with couplers or colorationmodifiers, the latter being selected in particular from aromaticmeta-diamines, meta-aminophenols, meta-diphenols and certainheterocyclic compounds, such as indole compounds.

[0004] The variety of molecules employed as oxidation bases and couplersmakes it possible to obtain a wide range of colours.

[0005] The “permanent” coloration obtained by means of these oxidationdyes is required, moreover, to meet a certain number of requirements.Hence it must have no toxicological drawbacks, must allow shades of thedesired intensity to be obtained, and must have good resistance toexternal agents (light, inclement weather, washing, permanent-waving,perspiration and friction).

[0006] The dyes must also allow white hair to be covered and, finally,they must be as unselective as possible; in other words, they must allowthe smallest possible differences in coloration to be produced over theentire length of a single keratinous fibre, which may in fact besensitized (i.e. damaged) differently between its tip and its root.

[0007] The Applicant has now discovered that it is possible to obtainnew, powerful dyes, of low selectivity and particularly high resistance,which are capable of giving rise to intense colorations in variousshades, using pyrrolo-azole compounds as couplers in the presence of anoxidation base.

[0008] It is this discovery which forms the basis of the presentinvention.

[0009] The invention provides a composition for the dyeing of keratinousfibres and, in particular, of human keratinous fibres, such as hair,which is characterized in that it comprises, in a medium appropriate fordyeing:

[0010] as coupler, at least one pyrrolo-azole compound corresponding toone of the following formulae (I) and (II), or one of its addition saltswith an acid:

[0011] in which:

[0012] R₁ is: a hydrogen atom; a halogen atom such as bromine, chlorineor fluorine; an acetylamido group; an alkoxy radical (such as, forexample: methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy,phenoxyethoxy, 2-cyanoethoxy, phenethyloxy, p-chlorobenzyloxy ormethoxyethylcarbamoylmethoxy); an aryloxy radical (such as, for example:phenoxy, 4-methoxyphenoxy, 4-nitrophenoxy, 4-cyanophenoxy,4-methanesulphonamidophenoxy, 4-methanesulphonylphenoxy, 3-methylphenoxyor 1-naphthyloxy); an acyloxy radical (such as, for example: acetoxy,propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyalkyloxy,pyruvyloyloxy, cinnamoyloxy or myristoyloxy); an arylthio radical (suchas, for example: phenylthio, 4-carboxyphenylthio,2-ethoxy-5-tert-butylphenylthio, 2-carboxyphenylthio or4-methanesulphonylphenylthio); an alkylthio radical (such as, forexample: methylthio, ethylthio, propylthio, butylthio, 2-cyanoethylthio,benzylthio, phenethylthio, 2-(diethylamino)ethylthio, ethoxyethylthio orphenoxyethylthio); a heteroarylthio radical (such as, for example:5-phenyl-2,3,4,5-tetrazolylthio, 2-benzothiazolylthio); a heteroaryloxyradical (such as, for example: 5-phenyl-2,3,4,5-tetrazolyloxy or2-benzothiazolyloxy); a thiocyano radical; anN,N-diethylthiocarbonylthio radical; a dodecyloxythiocarbonylthioradical; a benzenesulphonamido radical; an N-ethyltoluenesulphonamidoradical; a pentafluorobutanamido radical; a2,3,4,5,6-pentafluorobenzamido radical; a p-cyanophenylureido radical;an N,N-diethylsulphamoylamino radical; a pyrazolyl radical; animidazolyl radical; a triazolyl radical; a tetrazolyl radical; abenzimidazolyl radical; a 1-benzyl-5-ethoxy-3-hydantoinyl radical; a1-benzyl-3-hydantoinyl radical; 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl; a2-oxy-1,2-dihydro-1-pyridinyl radical; an alkylamido; an arylamido; aradical NR^(III)R^(IV) where R^(III) and R^(IV) are identical ordifferent and are a C₁-C₄ alkyl; a hydroxyalkyl; a carboxyl; or analkoxycarboxyl radical;

[0013] R₂ and R₃ are independently of one another a hydrogen atom; ahalogen atom (such as bromine, chlorine or fluorine); a linear orbranched C₁-C₅ alkyl radical which is optionally substituted by one ortwo halogen, hydroxyl, alkoxy, aryloxy, amino, alkylamino, acyl oracylamino radicals; a C₁-C₄ alkoxy radical; a C₁-C₄ alkylthio radical;an arylthio radical; a benzylthio radical; an acyl radical (such asacetyl, 3-phenylpropanoyl, benzoyl or 4-dodecyloxybenzoyl); an acylaminoradical; an acyloxy radical (such as acetoxy); a carbamoyl radical (suchas carbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N,N-dibutylcarbamoylor N-(2-dodecyloxyethyl)carbamoyl); a phenyl radical which is optionallysubstituted by one or two halogen, nitro, sulphonyl, C₁-C₄ alkoxy, C₁-C₄alkyl, C₁-C₃ trifluoroalkyl, amino or alkylamino groups; analkoxycarbonyl radical (such as methoxycarbonyl, ethoxycarbonyl,isopropyloxycarbonyl, tert-butyloxycarbonyl, isobutyloxycarbonyl,butylcarbamoylethoxycarbonyl or perfluorohexylethoxycarbonyl); anaryloxycarbonyl radical (such as phenoxycarbonyl or2,5-diamylphenoxycarbonyl); a cyano radical; a nitro radical; adialkylphosphono radical (such as dimethylphosphono); a diarylphosphonoradical (such as diphenylphosphono); a dialkoxyphospholyl radical (suchas dimethoxyphospholyl); a dialkylphosphinyl radical (such asdimethylphosphinyl); a diarylphosphinyl radical (such asdiphenylphosphinyl); an alkylsulphinyl radical (such as3-phenoxypropylsulphinyl); an arylsulphinyl radical (such as3-phenoxypropylsulphinyl); an arylsulphonyl radical (such asbenzenesulphonyl or toluenesulphonyl); an alkylsulphonyl radical(methanesulphonyl, octanesulphonyl); a sulphonyloxy radical (such asmethanesulphonyloxy or toluenesulphonyloxy); an acylthio radical (suchas acetylthio or benzoylthio); a sulphamoyl radical (such asN-ethylsulphamoyl, N,N-diisopropylsulphamoyl or N,N-diethylsulphamoyl);a thiocyanate radical; or a thiocarbonyl radical (such asmethylthiocarbonyl or phenylthiocarbonyl);

[0014] Z_(a), Z_(b) and Z_(c) are independently of one another anitrogen atom or a carbon atom carrying a radical R₄, R₅, R₆ or R₇;

[0015] R₄, R₆ and R₇ are identical or different and are a hydrogen atom;a linear or branched C₁-C₂₀ alkyl radical which is optionallysubstituted by 1 or 2 radicals R selected from the group consisting ofhalogen, nitro, cyano, hydroxyl, alkoxy, aryloxy, amino, alkylamino,acylamino, carbamoyl, sulphonamido, sulphamoyl, imido, alkylthio,arylthio, aryl, alkoxycarbonyl and acyl; an aryl radical (such as phenylor naphthyl) which is optionally substituted by 1 or 2 radicals R asdefined above; a 5- or 6-membered heterocycle having at least onenitrogen, oxygen or sulphur atom (such as pyridyl, quinolyl, pyrrolyl,morpholyl, furyl, tetrahydrofuryl, pyrazolyl, triazolyl, tetrazolyl,thiazolyl, oxazolyl, imidazolyl or thiadiazolyl) and being optionallysubstituted by 1 or 2 radicals R as defined above;

[0016] when R₄, R₆ and R₇ are an alkyl radical, an aryl radical or a 5-or 6-membered heterocycle (defined above), the radical or heterocyclemay be attached to the carbon atom of the ring system via an oxygen,nitrogen or sulphur atom (in this case, R₄, R₆ and R₇ become XR₄, XR₆ orXR₇ where X=O, NH, S);

[0017] R₄, R₆ and R₇ may also be a halogen atom (such as bromine,chlorine or fluorine); an acyl radical; a sulphonyl radical; a sulphinylradical; a phosphonyl radical; a carbamoyl radical,; a sulphamoylradical; a cyano radical; a siloxy radical; an amino radical; anacylamino radical; an acyloxy radical; a carbamoyloxy radical; asulphonamide radical; an imide radical; a ureido radical; asulphamoylamino radical; an alkoxycarbonylamino radical; anaryloxycarbonylamino radical; an alkoxycarbonyl radical; anaryloxycarbonyl radical; or a carboxyl radical;

[0018] R₅ is hydrogen; halogen; an acyl radical; an acyloxy radical; acarbamoyl radical; an alkoxycarbonyl radical; a cyano radical; a nitroradical; a dialkylphosphono radical; a diarylphosphono radical; adialkoxyphospholyl radical; a dialkylphosphinyl radical; adiarylphosphinyl radical; an alkylsulphinyl radical; an arylsulphinylradical; an alkylsulphonyl radical; an arylsulphonyl radical; asulphonyloxy radical; an acylthio radical; a sulphamoyl radical; athiocyanate radical; a thiocarbonyl radical; a haloaryloxy radical (suchas pentafluorophenyloxy); a haloalkylamino (such asN,N-di(trifluoromethylamino)); a haloalkylthio (such asdifluoromethylthio); an aryl which is unsubstituted or substituted byelectron-withdrawing groups (for example Cl, NO₂, F); or a heterocycle(such as 2-benzoxazolyl, 2-benzothiazolyl, pyrazolyl,5-chloro-1-tetrazolyl or 1-pyrrolyl);

[0019] and at least one oxidation base.

[0020] Among the radicals R₁ of formulae (I) and (II) preference isgiven to radicals selected from the group consisting of:

[0021] a hydrogen atom; a C₁-C₄ alkoxy; phenoxy; phenoxy substituted bya halogen atom, a C₁-C₄ alkyl, a carboxyl or a trifluoromethyl group; anacyloxy radical; benzyloxy; C₁-C₄ alkylthio; phenylthio; phenylthiosubstituted by a halogen atom, a C₁-C₄ alkyl, a carboxyl or atrifluoromethyl group; a C₁-C₄ alkylamido; phenylamido; a radicalNR^(III)R^(IV) where R^(III) and R^(IV) are identical or different andare a C₁-C₄ alkyl, a C₁-C₄ hydroxyalkyl; a carboxyl or a C₁-C₄alkoxycarboxyl radical.

[0022] Among the radicals R₁ of the formulae (I) and (II) defined above,particular preference is given to radicals selected from the groupconsisting of: hydrogen; chlorine or bromine; methoxy or ethoxy;phenyloxy; 4-methylphenyloxy; acyloxy; benzyloxy; methylthio orethylthio; phenylthio; 4-methylphenylthio; 2-tert-butylphenylthio;acetamido; phenylacetamido; dimethylamino; diethylamino;ethylmethylamino; and (β-hydroxyethyl)methylamino.

[0023] In addition, very particular preference is given to radicals R₁selected from the group consisting of: hydrogen; chlorine; ethoxy;phenoxy; benzyloxy; acyloxy; acetamido; and dimethylamino.

[0024] Among the radicals R₂ and R₃ of the formulae (I) and (II),preference is given to radicals selected from the group consisting of:

[0025] acyl; acyloxy; carbamoyl; alkoxycarbonyl; aryloxycarbonyl; cyano;nitro; alkylsulphinyl; arylsulphinyl; alkylsulphonyl; arylsulphonyl;sulphamoyl; haloalkyl; C₁-C₄ alkyl; and hydrogen.

[0026] Among the radicals R₂ and R₃ of the formulae (I) and (II) definedabove, particular preference is given to radicals selected from thegroup consisting of:

[0027] acyl (such as acetyl, ethylcarbonyl or phenylcarbonyl);alkoxycarbonyl (such as methoxy- or ethoxycarbonyl); nitro; cyano;arylsulphonyl (such as phenylsulphonyl); carbamoyl (such as carbamoyl orN-ethylcarbamoyl); haloalkyl (such as trifluoromethyl); hydrogen; andC₁-C₄ alkyl (such as methyl or ethyl).

[0028] In addition, very particular preference is given to radicals R₂selected from the group consisting of: cyano; hydrogen; methyl; andphenyl, and to the radicals R₃ selected from the group consisting of:alkoxycarbonyl, such as methoxycarbonyl or ethoxycarbonyl;aryloxycarbonyl; hydrogen; methyl; and cyano.

[0029] Among the radicals R₄, R₆ and R₇ of the formulae (I) and (II),preference is given to radicals selected from the group consisting of:

[0030] a linear or branched C₁-C₄ alkyl radical; aryl, such as phenyl;phenyl substituted by a halogen, a methoxy radical, a nitro group, acyano group, a trifluoromethyl group or an amino group; cyano; nitro;acylamino; arylamino; alkylthio, such as methylthio or ethylthio;arylthio, such as phenylthio; carbamoyl, such as carbamoyl orN-ethylcarbamoyl; sulphonyl, such as methylsulphonyl; alkoxycarbonyl,such as methoxycarbonyl or ethyloxycarbonyl; aryloxycarbonyl, such asphenoxycarbonyl; acyl, such as acetyl or ethylcarbonyl; and hydrogen.

[0031] Additionally, very particular preference is given to the radicalsR₄, R₆ and R₇ of the formulae (I) and (II) selected from the groupconsisting of:

[0032] hydrogen; linear or branched C₁-C₄ alkyl (such as methyl, ethylor isopropyl); aryl, such as phenyl; and phenyl substituted by ahalogen, a methoxy radical, a nitro group, a cyano group, atrifluoromethyl group or an amino group.

[0033] Among the radicals R₅ of the formulae (I) and (II) defined above,particular preference is given to radicals selected from the groupconsisting of:

[0034] acyl (such as acetyl, benzoyl or ethylcarbonyl); alkoxycarbonyl(such as methoxy- or ethoxycarbonyl or isopropoxycarbonyl);aryloxycarbonyl such as phenoxycarbonyl; nitro; cyano; arylsulphonyl(such as phenylsulphonyl); haloalkyl (such as trifluoromethyl); and ahydrogen.

[0035] Additionally, very particular preference is given to the radicalsR₅ selected from the group consisting of: cyano; alkoxycarbonyl (such asmethoxy- or ethoxycarbonyl); aryloxycarbonyl, such as phenoxycarbonyl;haloalkyl (such as trifluoromethyl); and a hydrogen.

[0036] Among the preferred compounds of the invention corresponding tothe formula (I), mention may be made of those selected from the groupconsisting of:

[0037] (i) the pyrrolo[1,2-b]-1,2,4-triazoles of formula:

[0038] (ii) the pyrrolo[2,1-c]-1,2,4-triazoles of formula:

[0039] in which R₁, R₂, R₃ and R₄ are as defined above.

[0040] As examples of compounds of formula (Ia), particular mention maybe made of those for which:

[0041] R₁ is hydrogen or chlorine;

[0042] R₂ and R₃ are, respectively: cyano and cyano; ethyloxycarbonyland cyano; trifluoromethyl and cyano; phenylsulphonyl and cyano;trifluoromethyl and ethyloxycarbonyl; ethyloxycarbonyl andethyloxycarbonyl; methyloxycarbonyl and methyloxycarbonyl; hydrogen andhydrogen; or hydrogen and methyl; and

[0043] R₄ is methyl, ethyl, isopropyl, phenyl or hydrogen.

[0044] Among the compounds of formula (Ia) above, very particularmention may be made of:

[0045] 3,4-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole,

[0046] 3,4-dicyano-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,

[0047] 3,4-dicyano-8-tert-butylpyrrolo[1,2-b]-1,2,4-triazole,

[0048] 5-chloro-3,4-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole,

[0049] and their addition salts with an acid.

[0050] As examples of compounds of formula (Ib) particular mention maybe made of those for which:

[0051] R₁ is hydrogen or chlorine;

[0052] R₂ and R₃ are simultaneously cyano or hydrogen; and

[0053] R₄ is methyl, ethyl, isopropyl, phenyl or hydrogen.

[0054] Among the compounds of formula (Ib) above, very particularmention may be made of:

[0055] 5,6-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,

[0056] 7-chloro-5,6-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,

[0057] and their addition salts with an acid.

[0058] Among the preferred compounds of the invention corresponding toformula (II), mention may be made of those selected from the groupconsisting of:

[0059] a) the pyrrolo[1,2-b]-1,2,4-triazoles of formula:

[0060] b) the pyrrolo[2,1-c]-1,2,4-triazoles of formula:

[0061] c) the pyrrolo[1,2-c]imidazoles of formula:

[0062] d) the pyrrolo[1,2-e]tetrazoles of formula:

[0063] e) the pyrrolo[1,2-a]pyrroles of formula:

[0064] f) the pyrrolo[1,2-a]imidazoles of formula:

[0065] g) the pyrrolo[1,2-c]-1,2,3-triazoles of formula:

[0066] in which R₄, R₅, R₆ and R₇ are as defined above.

[0067] As examples of compounds of formula (IIa), mention may be made inparticular of those for which:

[0068] R₁ is hydrogen or chlorine;

[0069] R₂ and R₃ are, respectively: methoxycarbonyl and cyano;ethyloxycarbonyl and cyano; cyano and methoxycarbonyl or ethoxycarbonyl;cyano and trifluoromethyl; cyano and phenylsulphonyl; methyloxycarbonyland methyloxycarbonyl; hydrogen and hydrogen; hydrogen and methyl;trifluoromethyl and cyano or trifluoromethyl and methyloxycarbonyl;carboxyl and cyano; cyano and cyano; ethyloxycarbonyl andethyloxycarbonyl; phenyl and cyano; methyl and hydrogen; and

[0070] R₄ is methyl, ethyl, isopropyl, phenyl or hydrogen.

[0071] Among the compounds of formula (IIa) above, very particularmention may be made of:

[0072] 5-cyano-4-ethoxycarbonyl-8-methylpyrrolo[1,2-b]-1,2,4-triazole,

[0073] 5-cyano-4-carboxy-8-methylpyrrolo[1,2-b]-1,2,4-triazole,

[0074] 4,5-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole,

[0075] 5-cyano-8-methyl-4-phenylpyrrolo[1,2-b]-1,2,4-triazole,

[0076] 4,8-dimethylpyrrolo[1,2-b]-1,2,4-triazole,

[0077] 4,5-di(ethyloxycarbonyl)-8-methylpyrrolo[1,2-b]-1,2,4-triazole,

[0078]3-chloro-5-cyano-4-ethoxycarbonyl-8-methylpyrrolo-[1,2-b]-1,2,4-triazole,

[0079] 5-cyano-4-ethoxycarbonyl-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,

[0080] 5-cyano-4-carboxy-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,

[0081] 4,5-dicyano-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,

[0082] 4,5-di(ethyloxycarbonyl)-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,

[0083]3-chloro-5-cyano-4-ethoxycarbonyl-8-phenylpyrrolo-[1,2-b]-1,2,4-triazole,

[0084]4-cyano-5-carboxy-8-(2-nitro-5-hydroxyphenyl)pyrrolo-[1,2-b]-1,2,4-triazole,

[0085] and their addition salts with an acid.

[0086] As examples of compounds of formula (IIIb), mention may be madein particular of those for which:

[0087] R₁ is hydrogen or chlorine;

[0088] R₂ and R₃ are, respectively: cyano and methoxycarbonyl;methoxycarbonyl and cyano; methoxycarbonyl and methoxycarbonyl; hydrogenand hydrogen or hydrogen and methyl; cyano and cyano; ethyloxycarbonyland ethyloxycarbonyl; phenyl and cyano; tert-butyl and cyano; and

[0089] R₄ is methyl, ethyl, isopropyl, phenyl or hydrogen.

[0090] Among the compounds of formula (IIb) above, very particularmention may be made of:

[0091] 6,7-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,

[0092] 5-chloro-6,7-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,

[0093] 6,7-di(ethyloxycarbonyl)-3-methylpyrrolo[2,1-c]-1,2,4-triazole,

[0094] 7-cyano-3-methyl-6-phenylpyrrolo[2,1-c]-1,2,4-triazole,

[0095] 7-cyano-3-methyl-6-tert-butylpyrrolo[2,1-c]-1,2,4-triazole,

[0096] and their addition salts with an acid.

[0097] As examples of compounds of formula (IIc), particular mention maybe made of those for which:

[0098] R₁ is acetamido, chlorine or hydrogen;

[0099] R₂ and R₃ are, respectively: methoxycarbonyl and cyano; or cyanoand cyano;

[0100] R₄ is hydrogen; and

[0101] R₅ is cyano.

[0102] Among the compounds of the formula (IIc) above, very particularmention may be made of:

[0103] 6,8-dicyano-5-ethoxycarbonylpyrrolo[1,2-c]imidazole,

[0104] 4-chloro-6,8-dicyano-5-ethoxycarbonylpyrrolo[1,2-c]-imidazole,

[0105] and their addition salts with an acid.

[0106] As examples of compounds of formula (IId), particular mention maybe made of those for which:

[0107] R₁ is hydrogen or chlorine; and

[0108] R₂ and R₃ are, respectively: cyano and methoxycarbonyl; cyano andcyano; methoxycarbonyl and cyano; methoxycarbonyl and methoxycarbonyl;hydrogen and hydrogen or hydrogen and methyl.

[0109] Among the compounds of formula (IId) above, very particularmention may be made of:

[0110] 6,7-dicyanopyrrolo[1,2-e]tetrazole,

[0111] 6-cyano-7-ethoxycarbonylpyrrolo[1,2-e]tetrazole,

[0112] 5-chloro-6,7-dicyanopyrrolo[1,2-e]tetrazole,

[0113] and their addition salts with an acid.

[0114] As examples of compounds of formula (IIe), particular mention maybe made of those for which:

[0115] R₁ is hydrogen or chlorine;

[0116] R₂ and R₃ are, respectively: cyano and methoxycarbonyl;

[0117] R₅ is trifluoromethyl;

[0118] R₆ is phenyl or methyl; and

[0119] R₇ is methyl.

[0120] As examples of compounds of formula (IIf), particular mention maybe made of those for which:

[0121] R₁ is hydrogen or chlorine; and

[0122] R₂, R₃, R₆ and R₇ are, respectively:

[0123] methoxycarbonyl/cyano/cyano/phenyl;

[0124] cyano/methoxycarbonyl/cyano/phenyl;

[0125] cyano/methoxycarbonyl/methoxycarbonyl/phenyl;

[0126] hydrogen/hydrogen/hydrogen/hydrogen; or

[0127] hydrogen/hydrogen/methyl/methyl.

[0128] Among the compounds of formula (IIf) above, very particularmention may be made of:

[0129] 2,3,7-tricyano-6-methylpyrrolo[1,2-a]imidazole,

[0130] 2,3,7-tricyano-6-trifluoromethylpyrrolo[1,2-a]-imidazole,

[0131] 2,3,7-tricyano-6-tert-butylpyrrolo[1,2-a]imidazole,

[0132] 2,3,7-tricyano-6-phenylpyrrolo[1,2-a]imidazole,

[0133] 2,3,7-tricyano-6-ethoxycarbonylpyrrolo[1,2-a]-imidazole,

[0134] 5-chloro-2,3,7-tricyano-6-tert-butylpyrrolo[1,2-a]-imidazole,

[0135] 5-chloro-2,3,7-tricyano-6-phenylpyrrolo[1,2-a]-imidazole,

[0136] 7-cyano-6-ethoxycarbonylpyrrolo[1,2-a]benzimidazole,

[0137] 7-cyano-6-phenylpyrrolo[1,2-a]benzimidazole,

[0138] 7-amido-6-ethoxycarbonylpyrrolo[1,2-a]benzimidazole,

[0139] and their addition salts with an acid.

[0140] As examples of compounds of formula (IIg), particular mention maybe made of those for which:

[0141] R₁ is hydrogen or chlorine;

[0142] R₂ is cyano;

[0143] R₃ is methoxycarbonyl; or ethyloxycarbonyl; and

[0144] R₅ is cyano.

[0145] Among the compounds of formula (IIg) above, very particularmention may be made of:

[0146] 5,6,8-tricyanopyrrolo[1,2-c]-1,2,3-triazole,

[0147] 5,8-dicyano-6-ethoxycarbonylpyrrolo[1,2-c]-1,2,3-triazole,

[0148]4-chloro-5,8-dicyano-6-ethoxycarbonylpyrrolo[1,2-c]-1,2,3-triazole,

[0149] and their addition salts with an acid.

[0150] The acid addition salts of the compounds of the invention can beselected in particular from hydrochlorides, hydrobromides, tartrates,tosylates, benzenesulphonates, sulphates, lactates and acetates.

[0151] The compounds of the present invention, their synthesisintermediates and the processes for their preparation are described inthe patents and patent applications U.S. Pat. No. 5,256,526, EP-A-557851, EP-A-578 248, EP-A-518 238, EP-A-456 226, EP-A-488 909, EP-A-488248 and in the following publications:

[0152] D. R. Liljegren, Ber. 1964, 3436;

[0153] E. J. Browne, J.C.S., 1962, 5149;

[0154] P. Magnus, J.A.C.S., 1990, 112, 2465;

[0155] P. Magnus, J.A.C.S., 1987, 109, 2711;

[0156] Angew. Chem. 1960, 72, 956;

[0157] and Rec. Trav. Chim. 1961, 80, 1075.

[0158] The compound or compounds of formula (I) or (II) make uppreferably between 0.0005 and 12% by weight, approximately, of the totalweight of the dyeing composition and, more particularly, between 0.005and 6% by weight.

[0159] The nature of the oxidation base or bases which can be employedin the dyeing composition according to the invention is not critical.This or these oxidation base or bases are preferably selected frompara-phenylenediamines, bisphenylalkylenediamines, para-aminophenols,ortho-aminophenols, heterocyclic bases, and their addition salts with anacid.

[0160] Among the para-phenylenediamines which can be employed asoxidation bases in the dyeing composition according to the invention,particular mention may be made of the compounds corresponding to thefollowing formula (III) and their addition salts with an acid:

[0161] in which:

[0162] R₈ is a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ monohydroxyalkyl,C₂-c₄ polyhydroxyalkyl or C₁-C₄-alkoxy-C₁-C₄-alkyl radical,

[0163] R₉ is a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ monohydroxyalkyl orC₂-C₄ polyhydroxyalkyl radical,

[0164] R₁₀ is a hydrogen atom, a halogen atom, such as a chlorine atom,or a C₁-C₄ alkyl, sulpho, carboxyl, C₁-C₄ monohydroxyalkyl or C₁-C₄hydroxyalkoxy radical, and

[0165] R₁₁ is a hydrogen atom or a C₁-C₄ alkyl radical.

[0166] In the formula (III) above, and when R₁₀ is other than a hydrogenatom, R₈ and R₉ are preferably a hydrogen atom and R₁₁ is preferably thesame as R₁₁, and, when R₁₀ is a halogen atom, R₈, R₉ and R₁₀ arepreferably a hydrogen atom.

[0167] Among the para-phenylenediamines of the formula (III) above, moreparticular mention may be made of para-phenylenediamine,para-tolylenediamine, 2-isopropyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-amino-1-(β-methoxyethyl)aminobenzene and2-chloro-para-phenylenediamine, and their addition salts with an acid.

[0168] Among the bisphenylalkylenediamines which can be employed asoxidation bases in the dyeing composition according to the invention,particular mention may be made of the compounds corresponding to thefollowing formula (IV) and their addition salts with an acid:

[0169] in which:

[0170] Q₁ and Q₂ are identical or different and are a hydroxyl radicalor a radical NHR₁₅ in which R₁₅ is a hydrogen atom or a C₁-C₄ alkylradical,

[0171] R₁₂ is a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ monohydroxyalkylor C₂-C₄ polyhydroxyalkyl radical or a C₁-C₄ aminoalkyl radical whoseamino moiety may be substituted,

[0172] R₁₃ and R₁₄ are identical or different and are a hydrogen orhalogen atom or a C₁-C₄ alkyl radical,

[0173] W is a radical taken from the group consisting of the followingradicals:

—(CH₂)_(n); —(CH₂)_(m)—O—(CH₂)_(m); —(CH₂)_(m)—CHOH—(CH₂)_(m)

[0174] and

[0175] in which n is an integer from 0 to 8 inclusive and m is aninteger from 0 to 4 inclusive.

[0176] Among the bisphenylalkylenediamines of formula (IV) above, moreparticular mention may be made ofN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diamino-2-propanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine andN,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine, andtheir addition salts with an acid.

[0177] Among these bisphenylalkylenediamines of formula (IV),N,N′-bis(β-hydroxyethyl)-N,N′-bis-(4′-aminophenyl)-1,3-diaminopropanol,or one of its addition salts with an acid, are particularly preferred.

[0178] Among the para-aminophenols which can be employed as oxidationbases in the dyeing composition according to the invention, particularmention may be made of the compounds corresponding to the followingformula (V) and their addition salts with an acid:

[0179] in which:

[0180] R₁₆ is a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ monohydroxyalkyl,C₁-C₄-alkoxy-C -C₄-alkyl or C₁-C₄ aminoalkyl radical, and

[0181] R₁₇ is a hydrogen or fluorine atom or a C₁-C₄ alkyl, C₁-c₄monohydroxyalkyl, C₂-c₄ polyhydroxyalkyl, C₁-C₄ aminoalkyl, C₁-c₄cyanoalkyl or C₁-C₄-alkoxy-C₁-C₄-alkyl radical,

[0182] it being understood that at least one of the radicals R₁₆ and R₁₇is a hydrogen atom.

[0183] Among the para-aminophenols of formula (V) above, more particularmention may be made of para-aminophenol, 4-amino-3-methylphenol,4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol and4-amino-2-(β-hydroxyethylaminomethyl)phenol, and their addition saltswith an acid.

[0184] Among the ortho-aminophenols which can be employed as oxidationbases in the dyeing composition according to the invention, particularmention may be made of 2-aminophenol, 2-amino-1-hydroxy-5-methylbenzene,2-amino-1-hydroxy-6-methylbenzene, and 5-acetamido-2-aminophenol, andtheir addition salts with an acid.

[0185] Among the heterocyclic bases which can be employed as oxidationbases in the dyeing composition according to the invention, particularmention may be made of pyridine derivatives, pyrimidine derivatives, andpyrazole derivatives, and their addition salts with an acid.

[0186] Among pyridine derivatives more particular mention may be made ofthe compounds described, for example, in the patents GB 1 026 978 and GB1 153 196, such as 2,5-diaminopyridine, and their addition salts with anacid.

[0187] Among pyrimidine derivatives more particular mention may be madeof the compounds described, for example, in the German patent DE 2 359399 or Japanese patents JP 88-571 and JP 91-333 495, such as2,4,5,6-tetraaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine, andtheir addition salts with an acid.

[0188] Among pyrazole derivatives more particular mention may be made ofthe compounds described in the patents DE 3 843 892 and DE 4 133 957 andpatent applications WO 94/08969 and WO 94/08970, such as4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole and1-(4′-chlorobenzyl)-4,5-diaminopyrazole, and their addition salts withan acid.

[0189] According to the invention, the oxidation base or bases make uppreferably from 0.0005 to 12% by weight, approximately, of the totalweight of the dyeing composition, and more preferably still from 0.005to 6% by weight, approximately, of this weight.

[0190] The dyeing composition according to the invention may alsoinclude one or more additional couplers other than the compounds offormula (I) and/or one or more direct dyes, so as to vary or enrich inglints the shades obtained with the oxidation bases.

[0191] The additional couplers which can be employed in the compositionaccording to the invention may be selected from the couplers employedconventionally in oxidation dyeing, among which particular mention maybe made of meta-phenylenediamines, meta-aminophenols, meta-diphenols andheterocyclic couplers such as, for example, indole derivatives andindoline derivatives, and their addition salts with an acid.

[0192] These couplers may be selected in particular from2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol,3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, sesamol, α-naphthol,6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole and6-hydroxyindoline, and their addition salts with an acid.

[0193] When present, these additional couplers make up preferably from0.0005 to 5% by weight, approximately, of the total weight of the dyeingcomposition, and more preferably still from 0.005 to 3% by weight,approximately, of this weight.

[0194] The acid addition salts of the oxidation base or bases and/or ofthe additional couplers which can be employed in the dyeing compositionof the invention are selected in particular from hydrochlorides,hydrobromides, sulphates and tartrates, lactates and acetates.

[0195] The medium appropriate for dyeing (or vehicle) consists generallyof water or of a mixture of water and at least one organic solvent forsolubilizing the compounds which would not be sufficiently soluble inwater. As organic solvent mention may be made, for example, of C₁-C₄lower alkanols, such as ethanol and isopropanol; glycerol; glycols andglycol ethers, such as 2-butoxyethanol, propylene glycol, propyleneglycol monomethyl ether, diethylene glycol monoethyl ether andmonomethyl ether, and aromatic alcohols, such as benzyl alcohol orphenoxyethanol, similar products, and mixtures thereof.

[0196] The solvents can be present in proportions of preferably between1 and 40% by weight, approximately, relative to the total weight of thedyeing composition, and more preferably still between 5 and 30% byweight, approximately.

[0197] The pH of the dyeing composition according to the invention isgenerally between 3 and 12. It can be adjusted to the desired valueusing acidifying or basifying agents commonly employed in dyeingkeratinous fibres.

[0198] Among the acidifying agents mention may be made, by way ofexample, of mineral or organic acids, such as hydrochloric acid,orthophosphoric acid, carboxylic acids, such as tartaric acid, citricacid and lactic acid, and sulphonic acids.

[0199] Among the basifying agents mention may be made, by way ofexample, of aqueous ammonia, alkali metal carbonates, alkanolamines suchas mono-, di- and triethanolamines, and derivatives thereof, sodiumhydroxide or potassium hydroxide, and the compounds of the followingformula (VI):

[0200] in which R is a propylene radical which is optionally substitutedby a hydroxyl group or a C₁-C₄ alkyl radical; R₁₈, R₁₉, R₂₀ and R₂₁ areidentical or different and are a hydrogen atom or a C₁-C₄ alkyl or C₁-C₄hydroxyalkyl radical.

[0201] The dyeing composition according to the invention may alsoinclude various adjuvants conventionally employed in hair dyecompositions, such as anionic, cationic, nonionic, amphoteric andzwitterionic surfactants or mixtures thereof, anionic, cationic,nonionic, amphoteric and zwitterionic polymers or mixtures thereof,organic or inorganic thickeners, antioxidants, penetration agents,sequestering agents, fragrances, buffers, dispersants, conditioners,such as silicones, for example, film formers, preservatives andopacifiers.

[0202] The person skilled in the art will of course take care to selectthe abovementioned optional complementary compound(s) such that theadvantageous properties intrinsic to the dyeing composition according tothe invention are not, or not substantially, impaired by the intendedaddition(s).

[0203] The dyeing composition according to the invention may be invarious forms, such as in the form of liquids, creams or gels or anyother form which is appropriate for dyeing keratinous fibres, andespecially human hair.

[0204] The invention also provides for the use of the compounds offormula (I) or (II) above, as coupler, in combination with at least oneoxidation base for the oxidation dyeing of keratinous fibres and, inparticular, of human keratinous fibres such as hair.

[0205] The invention additionally provides a method of oxidation-dyeingkeratinous fibres, and especially human keratinous fibres such as hair,employing the dyeing composition as defined above.

[0206] In accordance with this method, at least one dyeing compositionas defined above is applied to the fibres, the colour being developed atan acidic, neutral or alkaline pH with the aid of an oxidizing agentwhich is added just at the moment when the dyeing composition isemployed or which is present in an oxidizing composition which isapplied simultaneously or sequentially and separately.

[0207] According to a particularly preferred embodiment of the dyeingmethod according to the invention, the above-described dyeingcomposition is mixed at the time of use with an oxidizing compositionwhich comprises, in a medium appropriate for dyeing, at least oneoxidizing agent present in a quantity which is sufficient to develop acoloration. The resulting mixture is subsequently applied to thekeratinous fibres and is left to act for from 3 to 50 minutesapproximately, preferably from 5 to 30 minutes approximately, afterwhich the fibres are rinsed, shampooed, rinsed again and dried.

[0208] The oxidizing agent present in the oxidizing composition asdefined above may be selected from the oxidizing agents conventionallyemployed for the oxidation dyeing of keratinous fibres, among whichmention may be made of hydrogen peroxide, urea peroxide, alkali metalbromates, and persalts, such as perborates and persulphates. Hydrogenperoxide is particularly preferred.

[0209] The pH of the oxidizing composition comprising the oxidizingagent as defined above is such that, after it has been mixed with thedyeing composition, the pH of the resulting composition applied to thekeratinous fibres varies preferably between 3 and 12 approximately and,more preferably still, between 5 and 11. It is adjusted to the desiredvalue using acidifying or basifying agents which are commonly employedin dyeing keratinous fibres and are as defined above.

[0210] The oxidizing composition as defined above may also includevarious adjuvants which are conventionally employed in hair dyecompositions and are as defined above.

[0211] The composition which is ultimately applied to the keratinousfibres may be in various forms, such as in the form of liquids, creams,gels or any other form appropriate for dyeing keratinous fibres and, inparticular, human hair.

[0212] The invention also provides a multi-compartment dyeing device orkit, or any other multi-compartment packaging system, a firstcompartment of which contains the dyeing composition as defined aboveand a second compartment of which contains the oxidizing composition asdefined above. These devices can be equipped with a means permitting thedesired mixture to be delivered to the hair, such as the devicesdescribed in the patent FR-2 586 913 in the name of the Applicant.

EXAMPLES EXAMPLES 1 AND 2

[0213] DYEING IN AN ALKALINE MEDIUM

[0214] The following dyeing compositions according to the invention wereprepared (contents in grams): Example 1 25-cyano-4-ethoxycarbonyl-8-methyl- 0.654 0.654pyrrolo[1,2-b]-1,2,4-triazole (coupler) 4-amino-1-(β-methoxyethyl)amino-0.498 — benzene (oxidation base) 4,5-diamino-1,3-dimethylpyrazole —0.384 (oxidation base) Common dye vehicle No. 1 No. 1 Demineralizedwater q.s. 100 g 100 g

[0215] NB:5-cyano-4-ethoxycarbonyl-8-methylpyrrolo[1,2-b]-1,2,4-triazole wasprepared by the process described in patent application EP-A-518 238.Common dye vehicle No. 1 Ethanol   20 g Aqueous ammonia containing 20%NH₃   10 g Sodium metabisulphite 0.228 g Sequestering agent q.s.

[0216] Each of the dyeing compositions of Examples 1 and 2 above wasmixed at the time of use with an equal weight of a 20-volumes hydrogenperoxide solution (6% by weight).

[0217] Each of the resulting mixtures was applied for 30 minutes tolocks of natural grey hair containing 90% white hairs, permed orotherwise, in an amount of 10 g per g of hair. After rinsing, washingwith a standard shampoo and drying, the locks were dyed in the shadesindicated in Table 1 below: TABLE 1 Shade obtained on Shade obtained onnatural grey hair permed grey hair pH of the containing 90% containing90% Example mixture white hairs white hairs 1 9.9 Bottle green Bottlegreen 2 9.9 Coppery yellow Coppery orange

EXAMPLES 3 to 6

[0218] DYEING IN A NEUTRAL MEDIUM

[0219] The following dyeing compositions according to the invention wereprepared (contents in grams): Example 3 4 5 65-cyano-4-ethoxycarbonyl-8-methyl- 0.654 0.654 — —pyrrolo[1,2-b]-1,2,4-triazole (coupler)5-cyano-4-phenyl-8-methylpyrrolo- — — 0.666 — [1,2-b]-1,2,4-triazole(coupler) 7-amido-6-ethoxycarbonylpyrrolo- — — — 0.813[1,2-a]benzimidazole (coupler) 4-amino-1-(β-methoxyethyl)amino- 0.4980.498 0.498 0.498 benzene (oxidation base) Conmion dye vehicle No. 2 No.2 No. 2 No. 2 Demineralized water q.s. 100 g 100 g 100 g 100 g

[0220] NB: 5-cyano-4-phenyl-8-methylpyrrolo[1,2-b]-1,2,4-triazole wasprepared by the process described in the patent U.S. Pat. No. 5,256,526and 7-amido-6-ethoxycarbonyl-pyrrolo[1,2-a]benzimidazole was prepared bythe process described in the patent application EP-A-518 238. Common dyevehicle No. 2 Ethanol  20.0 g K₂HPO₄/KH₂PO₄ (1.5 M/1 M) buffer  10.0 gSodium metabisulphite 0.228 g Sequestering agent q.s.

[0221] Each of the dyeing compositions of Examples 3 and 6 above wasmixed at the time of use with an equal weight of a 20-volumes hydrogenperoxide solution (6% by weight).

[0222] Each of the dyeing compositions of Examples 4 and 5 above wasmixed at the time of use with an equal quantity by weight of a 6×10⁻³mol-% aqueous ammonium persulphate solution.

[0223] Each of the resulting mixtures was applied for 30 minutes tolocks of natural grey hair containing 90% white hairs, permed orotherwise, in an amount of 10 g per g of hair. After rinsing, washingwith a standard shampoo and drying, the locks were dyed in the shadesindicated in Table 2 below: TABLE 2 Shade obtained on Shade obtained onnatural grey hair permed grey hair pH of the containing 90% containing90% Example mixture white hairs white hairs 3 6.8 Green-bluish greyGreen-bluish grey 4 6.8 Blue-mauvish grey Blue-mauvish grey 5 6.8Mauvish blue Mauvish blue 6 6.8 Blue-greenish grey Blue-greenish grey

1. Composition for the dyeing of keratinous fibres and, in particular,of human keratinous fibres, such as hair, which is characterized in thatit comprises, in a medium appropriate for dyeing: as coupler, at leastone pyrrolo-azole compound or one of its addition salts with an acidcorresponding to one of the following formulae:

in which: R₁ is: a hydrogen atom; a halogen atom; an acetylamidoradical; an alkoxy radical; an aryloxy radical; an acyloxy radical; anarylthio radical; an alkylthio radical; a heteroarylthio radical; aheteroaryloxy radical; a thiocyano radical; anN,N-diethylthiocarbonylthio radical; a dodecyloxythiocarbonylthioradical; a benzenesulphonamido radical; an N-ethyltoluenesulphonamidoradical; a pentafluorobutanamido radical; a2,3,4,5,6-pentafluorobenzamido radical; a p-cyanophenylureido radical;an N,N-diethylsulphamoylamino radical; a pyrazolyl radical; animidazolyl radical; a triazolyl radical; a tetrazolyl radical; abenzimidazolyl radical; a 1-benzyl-5-ethoxy-3-hydantoinyl radical; a1-benzyl-3-hydantoinyl radical; 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl; a2-oxy-1,2-dihydro-1-pyridinyl radical; an alkylamido; an arylamido;acetylamido; a radical NR^(III)R^(IV) where R^(III) and R^(IV) areidentical or different and are a C₁-C₄ alkyl; a hydroxyalkyl; acarboxyl; or an alkoxycarboxyl radical; R₂ and R₃ independently of oneanother are a hydrogen atom; a halogen atom; a linear or branched C₁-C₅alkyl radical which is optionally substituted by one or two halogen,hydroxyl, alkoxy, aryloxy, amino, alkylamino, acyl or acylaminoradicals; a C₁-C₄ alkoxy radical; a C₁-C₄ alkylthio radical; an arylthioradical; a benzylthio radical; an acyl radical; an acylamino radical; anacyloxy radical; a carbamoyl radical; a phenyl radical which isoptionally substituted by one or two halogen, nitro, sulphonyl, C₁-C₄alkoxy, C₁-C₄ alkyl, C₁-C₃ trifluoroalkyl, amino or alkylamino groups;an alkoxycarbonyl radical; an aryloxycarbonyl radical; a cyano radical;a nitro radical; a dialkylphosphono radical; a diarylphosphono radical;a dialkoxyphospholyl radical; a dialkylphosphinyl radical; adiarylphosphinyl radical; an alkylsulphinyl radical; an arylsulphinylradical; an arylsulphonyl radical; an alkylsulphonyl radical; asulphonyloxy radical; an acylthio radical; a sulphamoyl radical; athiocyanate radical; or a thiocarbonyl radical; Z_(a), Z_(b) and Z_(c)are independently of one another a nitrogen atom or a carbon atomcarrying a radical R₄, R₅, R₆ or R₇; R₄, R₆ and R₇ are identical ordifferent and are a hydrogen atom; a linear or branched C₁-C₂₀ alkylradical which is optionally substituted by 1 or 2 radicals R selectedfrom the group consisting of halogen, nitro, cyano, hydroxyl, alkoxy,aryloxy, amino, alkylamino, acylamino, carbamoyl, sulphonamido,sulphamoyl, imido, alkylthio, arylthio, aryl, alkoxycarbonyl and acyl;an aryl radical which is optionally substituted by 1 or 2 radicals R asdefined above; a 5- or 6-membered heterocycle having at least onenitrogen, oxygen or sulphur atom and being optionally substituted by 1or 2 radicals R as defined above; when R₄, R₆ and R₇ are an alkylradical, an aryl radical or a 5- or 6-membered heterocycle (definedabove), the radical or heterocycle may be attached to the carbon atom ofthe ring system via an oxygen, nitrogen or sulphur atom (in this case,R₄, R₆ and R₇ become XR₄, XR₆ or XR₇ where X=O, NH, S); R₄, R₆ and R₇may also be a halogen atom; an acyl radical; a sulphonyl radical; asulphinyl radical; a phosphonyl radical; a carbamoyl radical; asulphamoyl radical; a cyano radical; a siloxy radical; an amino radical;an acylamino radical; an acyloxy radical; a carbamoyloxy radical; asulphonamide radical; an imide radical; a ureido radical; asulphamoylamino radical; an alkoxycarbonylamino radical; anaryloxycarbonylamino radical; an alkoxycarbonyl radical; anaryloxycarbonyl radical; or a carboxyl radical; R₅ is hydrogen; halogen;an acyl radical; an acyloxy radical; a carbamoyl radical; analkoxycarbonyl radical; a cyano radical; a nitro radical; adialkylphosphono radical; a diarylphosphono radical; adialkoxyphospholyl radical; a dialkylphosphinyl radical; adiarylphosphinyl radical; an alkylsulphinyl radical; an arylsulphinylradical; an alkylsulphonyl radical; an arylsulphonyl radical; asulphonyloxy radical; an acylthio radical; a sulphamoyl radical; athiocyanate radical; a thiocarbonyl radical; a haloaryloxy radical; ahaloalkylamino radical; a haloalkylthio; an aryl which is unsubstitutedor substituted by electron-withdrawing groups; or a heterocycle; and atleast one oxidation base.
 2. Composition according to claim 1 ,characterized in that the radicals R₁ of the formulae (I) and (II) areselected from the group consisting of: a hydrogen atom; a C₁-C₄ alkoxy;phenoxy; phenoxy substituted by a halogen atom, a C₁-C₄ alkyl, acarboxyl or a trifluoromethyl group; an acyloxy radical; benzyloxy;C₁-C₄ alkylthio; phenylthio; phenylthio substituted by a halogen atom, aC₁-C₄ alkyl, a carboxyl or a trifluoromethyl group; a C₁-C₄ alkylamido;phenylamido; a radical NR^(III)R^(IV) where R^(III) and R^(IV) areidentical or different and are a C₁-C₄ alkyl, a C₁-C₄ hydroxyalkyl; acarboxyl; and a C₁-C₄ alkoxycarboxyl radical.
 3. Composition accordingto claim 2 , characterized in that the radicals R₁ of the formulae (I)and (II) are selected from the group consisting of: hydrogen; chlorineor bromine; methoxy or ethoxy; phenyloxy; 4-methylphenyloxy; acyloxy;benzyloxy; methylthio or ethylthio; phenylthio; 4-methylphenylthio;2-tert-butylphenylthio; acetamido; phenylacetamido; dimethylamino;diethylamino; ethylmethylamino; and (β-hydroxyethyl)methylamino. 4.Composition according to claim 2 or 3 , characterized in that theradicals R₁ of the formulae (I) and (II) are selected from the groupconsisting of: hydrogen; chlorine; ethoxy; phenoxy; benzyloxy; acyloxy;acetamido; and dimethylamino.
 5. Composition according to any one ofclaims 1 to 4, characterized in that the radicals R₂ and R₃ of theformulae (I) and (II) are selected from the group consisting of: acyl;acyloxy; carbamoyl; alkoxycarbonyl; aryloxycarbonyl; cyano; nitro;alkylsulphinyl; arylsulphinyl; alkylsulphonyl; arylsulphonyl;sulphamoyl; haloalkyl; C₁-C₄ alkyl and hydrogen.
 6. Compositionaccording to claim 5 , characterized in that the radicals R₂ and R₃ ofthe formulae (I) and (II) are selected from the group consisting of:acyl; alkoxycarbonyl; nitro; cyano; arylsulphonyl; carbamoyl; haloalkyl;hydrogen; and C₁-C₄ alkyl.
 7. Composition according to claim 5 or 6 ,characterized in that the radicals R₂ of the formulae (I) and (II) areselected from the group consisting of: cyano; hydrogen; methyl; andphenyl and in that the radicals R₃ of the formulae (I) and (II) areselected from the group consisting of: alkoxycarbonyl, such asmethoxycarbonyl or ethoxycarbonyl; aryloxycarbonyl; hydrogen; methyl;and cyano.
 8. Composition according to any one of claims 1 to 7 ,characterized in that the radicals R₄, R₆ and R₇ of the formulae (I) and(II) are selected from the group consisting of: a linear or branchedC₁-C₄ alkyl radical; aryl; phenyl substituted by a halogen, a methoxyradical, a nitro group, a cyano group, a trifluoromethyl group or anamino group; cyano; nitro; acylamino; arylamino; alkylthio; arylthio;carbamoyl; sulphonyl; alkoxycarbonyl; aryloxycarbonyl; acyl andhydrogen.
 9. Composition according to claim 8 , characterized in thatthe radicals R₄, R₆ and R₇ of the formulae (I) and (II) are selectedfrom the group consisting of: hydrogen; linear or branched C₁-C₄ alkyl;aryl; phenyl substituted by a halogen, a methoxy radical, a nitro group,a cyano group, a trifluoromethyl group or an amino group. 10.Composition according to any one of claims 1 to 9 , characterized inthat the radicals R₅ of the formulae (I) and (II) are selected from thegroup consisting of: acyl; alkoxycarbonyl; aryloxycarbonyl; nitro;cyano; arylsulphonyl; haloalkyl; and hydrogen.
 11. Composition accordingto any one of claims 1 to 10 , characterized in that the radicals R₅ areselected from the group consisting of: cyano; alkoxycarbonyl;aryloxycarbonyl; haloalkyl; and a hydrogen.
 12. Composition according toany one of claims 1 to 11 , characterized in that the compounds offormula (I) are selected from the group consisting of: (i) thepyrrolo[1,2-b]-1,2,4-triazoles of formula:

(ii) the pyrrolo[2,1-c]-1,2,4-triazoles of formula:

in which R₁, R₂, R₃ and R₄ are as defined in any one of claims 1 to 11 .13. Composition according to claim 12 , characterized in that thecompounds of formula (Ia) are those for which: R₁ is hydrogen orchlorine; R₂ and R₃ are, respectively: cyano and cyano; ethoxycarbonyland cyano; trifluoromethyl and cyano; phenylsulphonyl and cyano;trifluoromethyl and ethyloxycarbonyl; ethoxycarbonyl and ethoxycarbonyl;methoxycarbonyl and methoxycarbonyl; hydrogen and hydrogen; or hydrogenand methyl; and R₄ is methyl, ethyl, isopropyl, phenyl or hydrogen. 14.Composition according to claim 12 , characterized in that the compoundsof formula (Ib) are those for which: R₁ is hydrogen or chlorine; R₂ andR₃ are simultaneously: cyano or hydrogen; and R₄ is methyl, ethyl,isopropyl, phenyl or hydrogen.
 15. Composition according to claim 12 ,characterized in that the compounds of formula (I) are selected from:3,4-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole,3,4-dicyano-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,3,4-dicyano-8-tert-butylpyrrolo[1,2-b]-1,2,4-triazole,5-chloro-3,4-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole,5,6-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,7-chloro-5,6-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole, and theiraddition salts with an acid.
 16. Composition according to any one ofclaims 1 to 11 , characterized in that the compounds of formula (II) areselected from the group consisting of: a) thepyrrolo[1,2-b]-1,2,4-triazoles of formula:

b) the pyrrolo[2,1-c]-1,2,4-triazoles of formula:

c) the pyrrolo[1,2-c]imidazoles of formula:

d) the pyrrolo[1,2-e]tetrazoles of formula:

e) the pyrrolo[1,2-a]pyrroles of formula:

f) the pyrrolo[1,2-a]imidazoles of formula:

g) the pyrrolo[1,2-c]-1,2,3-triazoles of formula:

in which R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined in any one ofclaims 1 to 10 .
 17. Composition according to claim 16 , characterizedin that the compounds of formula (IIa) are those for which: R₃ ishydrogen or chlorine; R₂ and R₃ are, respectively: methoxycarbonyl andcyano; ethyloxycarbonyl and cyano; cyano and methoxycarbonyl orethoxycarbonyl; cyano and trifluoromethyl; cyano and phenylsulphonyl;methyloxycarbonyl and methyloxycarbonyl; hydrogen and hydrogen; hydrogenand methyl; trifluoromethyl and cyano or trifluoromethyl andmethyloxycarbonyl; carboxyl and cyano; cyano and cyano; ethyloxycarbonyland ethyloxycarbonyl; phenyl and cyano; methyl and hydrogen; and R₄ ismethyl, ethyl, isopropyl, phenyl or hydrogen.
 18. Composition accordingto claim 16 , characterized in that the compounds of formula (IIb) arethose for which: R₁ is hydrogen or chlorine; R₂ and R₃ are,respectively: cyano and methoxycarbonyl; methoxycarbonyl and cyano;methoxycarbonyl and methoxycarbonyl; hydrogen and hydrogen or hydrogenand methyl; cyano and cyano; ethyloxycarbonyl and ethyloxycarbonyl;phenyl and cyano; tert-butyl and cyano; and R₄ is methyl, ethyl,isopropyl, phenyl or hydrogen.
 19. Composition according to claim 16 ,characterized in that the compounds of formula (IIc) are those forwhich: R₁ is acetamido, chlorine or hydrogen; R₂ and R₃ are,respectively: methoxycarbonyl and cyano; or cyano and cyano; R₄ ishydrogen; and R₅ is cyano.
 20. Composition according to claim 16 ,characterized in that the compounds of formula (IId) are those forwhich: R₁ is hydrogen or chlorine; and R₂ and R₃ are, respectively:cyano and methoxycarbonyl; cyano and cyano; methoxycarbonyl and cyano;methoxycarbonyl and methoxycarbonyl; hydrogen and hydrogen; or hydrogenand methyl.
 21. Composition according to claim 16 , characterized inthat the compounds of formula (IIe) are those for which: R₁ is hydrogenor chlorine; R₂ and R₃ are, respectively: cyano and methoxycarbonyl; R₅is trifluoromethyl; R₆ is phenyl or methyl; and R₇ is methyl. 22.Composition according to claim 16 , characterized in that the compoundsof formula (IIf) are those for which: R₁ is hydrogen or chlorine; andR₂, R₃, R₆ and R₇ are, respectively: methoxycarbonyl/cyano/cyano/phenyl;cyano/methoxycarbonyl/cyano/phenyl;cyano/methoxycarbonyl/methoxycarbonyl/phenyl;hydrogen/hydrogen/hydrogen/hydrogen; or hydrogen/hydrogen/methyl/methyl.23. Composition according to claim 16 , characterized in that thecompounds of formula (IIg) are those for which: R₁ is hydrogen orchlorine; R₂ is cyano; R₃ is methoxycarbonyl; or ethyloxycarbonyl; andR₅ is cyano.
 24. Composition according to claim 16 , characterized inthat the compounds of formula (II) are selected from:5-cyano-4-ethoxycarbonyl-8-methylpyrrolo[1,2-b]-1,2,4-triazole,5-cyano-4-carboxy-8-methylpyrrolo[1,2-b]-1,2,4-triazole,4,5-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole,5-cyano-8-methyl-4-phenylpyrrolo[1,2-b]-1,2,4-triazole,4,8-dimethylpyrrolo[1,2-b]-1,2,4-triazole,4,5-di(ethyloxycarbonyl)-8-methylpyrrolo[1,2-b]-1,2,4-triazole,3-chloro-5-cyano-4-ethoxycarbonyl-8-methylpyrrolo-[1,2-b]-1,2,4-triazole,5-cyano-4-ethoxycarbonyl-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,5-cyano-4-carboxy-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,4,5-dicyano-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,4,5-di(ethyloxycarbonyl)-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,3-chloro-5-cyano-4-ethoxycarbonyl-8-phenylpyrrolo-[1,2-b]-1,2,4-triazole,4-cyano-5-carboxy-8-(2-nitro-5-hydroxyphenyl)pyrrolo-[1,2-b]-1,2,4-triazole,6,7-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,5-chloro-6,7-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,6,7-di(ethyloxycarbonyl)-3-methylpyrrolo[2,1-c]-1,2,4-triazole,7-cyano-3-methyl-6-phenylpyrrolo[2,1-c]-1,2,4-triazole,7-cyano-3-methyl-6-tert-butylpyrrolo[2,1-c]-1,2,4-triazole,6,8-dicyano-5-ethoxycarbonylpyrrolo[1,2-c]imidazole,4-chloro-6,8-dicyano-5-ethoxycarbonylpyrrolo[1,2-c]-imidazole,6,7-dicyanopyrrolo[1,2-e]tetrazole,6-cyano-7-ethoxycarbonylpyrrolo[1,2-e]tetrazole,5-chloro-6,7-dicyanopyrrolo[1,2-e]tetrazole,2,3,7-tricyano-6-methylpyrrolo[1,2-a]imidazole,2,3,7-tricyano-6-trifluoromethylpyrrolo[1,2-a]-imidazole,2,3,7-tricyano-6-tert-butylpyrrolo[1,2-a]imidazole,2,3,7-tricyano-6-phenylpyrrolo[1,2-a]imidazole,2,3,7-tricyano-6-ethoxycarbonylpyrrolo[1,2-a]-imidazole,5-chloro-2,3,7-tricyano-6-tert-butylpyrrolo[1,2-a]-imidazole,5-chloro-2,3,7-tricyano-6-phenylpyrrolo[1,2-a]-imidazole,7-cyano-6-ethoxycarbonylpyrrolo[1,2-a]benzimidazole,7-cyano-6-phenylpyrrolo[1,2-a]benzimidazole,5,6,8-tricyanopyrrolo[1,2-c]-1,2,3-triazole,7-amido-6-ethoxycarbonylpyrrolo[1,2-a]benzimidazole,5,8-dicyano-6-ethoxycarbonylpyrrolo[1,2-c]-1,2,3-triazole,4-chloro-5,8-dicyano-6-ethoxycarbonylpyrrolo[1,2-c]-1,2,3-triazole, andtheir addition salts with an acid.
 25. Composition according to any oneof the preceding claims, characterized in that the acid addition saltsof the compounds of formula (I) or (II) are selected fromhydrochlorides, hydrobromides, tartrates, tosylates, benzenesulphonates,sulphates, lactates and acetates.
 26. Composition according to any oneof the preceding claims, characterized in that the compound or compoundsof formula (I) or (II) make up from 0.0005 to 12% by weight of the totalweight of the dyeing composition.
 27. Composition according to claim 26, characterized in that the compound or compounds of formula (I) or (II)make up from 0.0005 to 6% by weight of the total weight of the dyeingcomposition.
 28. Composition according to any one of the precedingclaims, characterized in that the oxidation base or bases are selectedfrom para-phenylenediamines, bisphenylalkylenediamines,para-aminophenols, ortho-aminophenols, terocyclic bases, and theiraddition salts with an acid.
 29. Composition according to any one of thepreceding claims, characterized in that the oxidation base or bases makeup from 0.0005 to 12% by weight, approximately, of the total weight ofthe dyeing composition.
 30. Composition according to claim 29 ,characterized in that the oxidation base or bases make up from 0.005 to6% by weight, approximately, of the total weight of the dyeingcomposition.
 31. Composition according to any one of the precedingclaims, characterized in that it also includes one or more additionalcouplers other than the compounds of formula (I) or (II) and/or one ormore direct dyes.
 32. Composition according to any one of the precedingclaims, characterized in that the medium appropriate for dyeing (orvehicle) consists of water or of a mixture of water and at least oneorganic solvent selected from C₁-C₄ lower alkanols, glycerol, glycolsand glycol ethers, aromatic alcohols, similar products, and mixturesthereof.
 33. Composition according to any one of the preceding claims,characterized in that it has a pH of between 3 and
 12. 34. Compositionaccording to any one of the preceding claims, characterized in that itis in the form of liquids, creams, gels or any other form appropriatefor dyeing keratinous fibres, and especially human hair.
 35. Use of thecompounds of formula (I) or (II) or their acid addition salts as definedin any one of claims 1 to 25 as couplers in compositions for theoxidation dyeing of keratinous fibres and, in particular, of humankeratinous fibres, such as hair, in combination with at least oneoxidation base.
 36. Method of oxidation-dyeing keratinous fibres and, inparticular, human keratinous fibres, such as hair, characterized in thatat least one dyeing composition as defined in any one of claims 1 to 34is applied to these fibres, the colour being developed at an acidic,neutral or alkaline pH with the aid of an oxidizing agent which is addedjust at the moment when the dyeing composition is employed or which ispresent in an oxidizing composition which is applied simultaneously orsequentially and separately.
 37. Method according to claim 36 ,characterized in that the oxidizing agent is selected from hydrogenperoxide, urea peroxide, alkali metal bromates, and persalts, such asperborates and persulphates.
 38. Multi-compartment device, ormulti-compartment dyeing kit, a first compartment of which contains adyeing composition as defined in any one of claims 1 to 34 , and asecond compartment of which contains an oxidizing composition.